Showing papers in "Fuels in 2022"

The Operating Parameters, Structural Composition, and Fuel Sustainability Aspects of PEM Fuel Cells: A Mini Review

Abstract: This mini review discusses the sustainability aspects of various fuels for proton exchange membrane fuel cells (PEMFCs). PEMFCs operate by converting the chemical energy in a fuel into electrical energy. The most crucial parameters in the operation process are the temperature, pressure, relative humidity, and air stoichiometry ratio, as presented in this work. The classical structure of a PEMFC consists of a proton exchange membrane, anode electrode, cathode electrode, catalyst layers (CLs), microporous layer (MPLs), gas diffusion layers (GDLs), two bipolar plates (BPs), and gas flow channels (GFCs). The mechanical behavior and the conductivity of the protons are highly dependent on the structure of the MEAs. This review discusses the various fuels and their production paths from sustainable sources. For the fuel production process to be renewable and sustainable, a hydrogen electrolyzer could be powered from solar energy, wind energy, geothermal energy, or hydroelectric energy, to produce hydrogen, which in turn could be fed into the fuel cell. This paper also reviews biomass-based routes for sustainable fuel production.

Torrefaction and Densification of Wood Sawdust for Bioenergy Applications

Abstract: In this study, wood sawdust as waste residue from wood processing mills was pretreated using torrefaction to improve fuel properties and densified to facilitate transportation. Sawdust was torrefied in a fixed bed reactor using inside temperatures (IT) of 230, 260 and 290 °C for 15, 30 and 45 min, residence time. Due to the low calorific value of the treatments, the outside temperature (OT) of the fixed bed reactor was used instead for a fixed duration of 45 min, which resulted in an increase in energy value by 40% for the most severe conditions. The mechanical strength of the pellets was enhanced by adding 20% binder (steam-treated spruce sawdust) to biochar, which improved the pellet tensile strength by 50%. Liquid by-products from the torrefaction process contained furfural and acetic acid, which can be separated for commercial uses. Thermochemical analysis showed better fuel properties of OT torrefied samples such as high fixed carbon (52%), low volatiles (41%) and lower oxygen contents (27%) compared to IT torrefied samples (18, 77 and 43%, respectively). Low moisture uptake of torrefied pellets compared to raw pellets, along with other attributes such as renewability, make them competent substitutes to fossil-based energy carriers such as coal.

Testing the Sediment Organic Contents Required for Biogenic Gas Hydrate Formation: Insights from Synthetic 3-D Basin and Hydrocarbon System Modelling

Abstract: Gas hydrates comprise one of the largest reservoirs of organic carbon on Earth. Marine gas hydrate predominantly consists of biogenic (i.e., microbially generated) methane molecules trapped within lattice-like cages of frozen water molecules. Sedimentary organic matter is the feedstock for methanogens producing gas in anaerobic sub-seafloor environments. Therefore, an understanding of the minimum amount of organic material (measured as carbon and hydrogen content) necessary for methanogenesis to result in appreciable volumes of hydrocarbons is central to understanding the requirements for gas hydrate formation. Reactive transport modelling by workers over the past 20 years suggests minimum requirements of ~0.3–0.5. wt. % TOC (total organic carbon) for gas hydrate formation, while earlier workers predicted TOC as low as ~0.1–0.2. wt. % could produce biogenic gas. However, the hydrogen content (recognized as the limiting reagent in hydrocarbon generation for over 50 years) needed for biogenic gas generation and gas hydrate formation is poorly understood. Furthermore, the minimum organic contents needed for gas hydrate formation have not been investigated via basin-scale computational modeling. Here, we construct a synthetic 3-D basin and gas hydrate system model to investigate minimum sediment TOC and hydrogen (HI, hydrogen index) contents needed for gas hydrate formation. Our modelling suggests that, under geologically favorable conditions, TOC as low as 0.1. wt. % (paired with 100 HI) and HI as low as 50 (paired with 0.2. wt. % TOC) may produce biogenic gas hydrate saturations above 1%. Our modelling demonstrates the importance of basin-scale investigation of hydrocarbon systems and demonstrates how the confluence of favorable structural controls (e.g., faults, folds, anticlines) and stratigraphic controls (e.g., carrier beds, reservoirs) can result in gas hydrate accumulations, even in organic-poor settings.

Ammonia Production Plants—A Review

Abstract: Considering the global scientific and industrial effort to utilize ammonia as an alternative to natural gas combustion to run power plants, it is crucial to objectively assess the literature before adjusting or proposing new and advancing techniques in ammonia plants while considering a variety of factors. As a result, this paper assesses the global effort to improve existing ammonia plants and identifies progress by evaluating the currently available dataset to identify knowledge gaps and highlight aspects that have yet to be addressed. Based on the literature reviewed in this study, it was found that the majority of the efforts to advance ammonia plants mainly focus on reducing energy consumption, implementing alternative methods to extract the necessary hydrogen and nitrogen in the process, and changing the cycle arrangement and operating conditions to make the industrial plants more compact. However, regarding carbon reduction in the ammonia production process, it is clear that the effort is less significant when compared to the global scientific and industrial progress in other areas.

Sediment Organic Contents Required for Gas Hydrate Formation: A Survey of Published Basin and Hydrocarbon System Models

Abstract: Recent advances in basin and petroleum system modelling have allowed for the investigation of gas hydrate systems, including modelling of the generation, migration, and accumulation of biogenic and thermogenic gas within gas hydrate deposits. In this brief survey paper, the treatment of sediment organic properties (organic content and richness, expressed as total organic carbon and the hydrogen index) within previously published basin and petroleum system models of marine gas hydrate systems is reviewed. Eight studies (published between 2015 and 2020) are described and discussed. This review contributes to the state of knowledge in the field by reviewing existing modelling studies of gas hydrates and concludes with brief takeaways on important considerations and knowledge gaps in the state of basin and hydrocarbon system modelling of gas hydrate systems.

Impact of Biochar Addition in Microwave Torrefaction of Camelina Straw and Switchgrass for Biofuel Production

Abstract: The possibility of applying biochar in mild torrefaction treatment to improve the thermochemical characteristics of ground biomass was the focus of the study. Camelina straw and switchgrass were torrefied in a reactor using microwave irradiation at torrefaction temperatures of 250 °C and 300 °C with residence times 10, 15 and 20 min, under nitrogen-activated inert conditions. Both biochar addition of more than 10% and residence time significantly affected the product yields, as MW torrefaction temperatures shifted from 250 °C to 300 °C. Overall, the results indicated a slight increase in ash content, mass loss percentage intensification, heating values, and fixed carbon, while moisture content and volatile matter decreased in camelina straw and switchgrass, with or without biochar. Biochar addition with a long residence time (20 min) at 250 °C reduced energy requirement during the microwave torrefaction process. The combustion index values showed that torrefied camelina straw or switchgrass with biochar addition suits co-combustion with coal in a coal-fired plant and is a potential biomaterial for biofuel pellets.

The Addition of Particles to an Alternative Jet Fuel

Abstract: The expansion of the research on nanoscale particles demonstrates several advantages in terms of stability and an increased surface area to volume ratio compared to micron-sized particles. Based on this, the present work explores the addition of aluminum particles in hydrotreated vegetable oil (HVO), an alternative jet fuel. To evaluate the influence of particle sizes, nano and micron particles (40 nm and 5 μm) in a particle concentration of 0.5 wt.% were stably suspended in HVO. This study evaluates droplet combustion with an initial diameter of 250 μm in a drop tube furnace under different furnace temperatures (600, 800, 1000 °C). A high magnification lens coupled with a high-speed camera provides qualitative and quantitative data regarding droplet size evolution and micro-explosions. Pure HVO and Jet A-1 were also tested for comparison purposes. The results reveal that the addition of aluminum particles enhances the alternative jet fuel combustion. Furthermore, decreasing the particle size and increasing the furnace temperature enhances the burning rate compared to the pure HVO. Pure HVO presents a burning rate nearly to 1.75 mm2/s until t/D02 = 0.35 s/mm2 at T = 1000 °C. When nanoparticles are added to HVO in a particle concentration of 0.5 wt.%, an improvement of 24% in burning rate is noticed. Conventional jet fuel and pure HVO do not present any disruptive burning phenomena. However, when aluminum particles were added to HVO, micro-explosions were detected at the end of droplet lifetime, regardless of the particle size.

Deflagration-to-Detonation Transition in Stochiometric Propane–Hydrogen–Air Mixtures

Abstract: Hydrocarbon–hydrogen blends are often considered as perspective environmentally friendly fuels for power plants, piston engines, heating appliances, home stoves, etc. However, the addition of hydrogen to a hydrocarbon fuel poses a potential risk of accidental explosion due to the high reactivity of hydrogen. In this manuscript, the detonability of stoichiometric C3H8–H2–air mixtures is studied experimentally in terms of the run-up time and distance of deflagration to detonation transition (DDT). The hydrogen volume fraction in the mixtures varied from 0 to 1. Three different configurations of detonation tubes were used to ensure the DDT in the mixtures of the various compositions. The measured dependences of the DDT run-up time and distance on the hydrogen volume fraction were found to be nonlinear and, in some cases, nonmonotonic with local maxima. Blended fuel detonability is shown to increase sharply only at a relatively large hydrogen volume fraction (above 70%), i.e., the addition of hydrogen to propane in amounts less than 70% vol. does not affect the detonability of the blended fuel significantly. The observed nonlinear/nonmonotonic dependences are shown to be the manifestation of the physicochemical properties of hydrogen-containing mixtures. An increase in the hydrogen volume fraction is accompanied by effects leading to both an increase and a decrease in mixture sensitivity to the DDT. Thus, on the one hand, the increase in the hydrogen volume fraction increases the mixture sensitivity to DDT due to an increase in the laminar flame velocity and a decrease in the self-ignition delay at isotherms above 1000 K and pressures relevant to DDT. On the other hand, the mixture sensitivity to DDT decreases due to the increase in the speed of sound in the hydrogen-containing mixture, thus leading to a decrease in the Mach number of the lead shock wave propagating ahead of the flame, and to a corresponding increase in the self-ignition delay. Moreover, for C3H8–H2–air mixtures at isotherms below 1000 K and pressures relevant to DDT, the self-ignition delay increases with hydrogen volume fraction.

Ultrasonication Assisted Catalytic Transesterification of Ceiba Pentandra (Kapok) Oil Derived Biodiesel Using Immobilized Iron Nanoparticles

Abstract: The embedded immobilized enzymes (Rhizopus-oryzae) on the magnetic nanoparticles (Fe3O4-NPs) is a new application for the sustainable production of high-quality biodiesel. In this study, biodiesel is derived from Kapok oil via ultrasonication (US)-assisted catalytic transesterification method. A novel attempt is made to prepare magnetic nanoparticles embedded by an immobilized enzyme to solve the problem of enzyme denaturation. This innovative method resulted in optimum biodiesel conversion of 89 ± 1.17% under reactant molar ratio (methanol: oil) of 6:1, catalyst loading 10 wt% with a reaction time of 4 h at 60 °C. The kinetic and thermal study reveals that conversion of Kapok oil to biodiesel follows a pseudo first-order reaction kinetic with a lower ΔE of 30.79 kJ mol−1. The ΔH was found to be 28.06 kJ mol−1 with a corresponding ΔS of −237.12 J mol−1 K−1 for Fatty Acid Methyl Ester formation. The ΔG was calculated to be from 102.28 to 109.40 kJ mol−1 for temperature from 313 K to 343 K. The positive value of ΔH and ΔG is an indication of endothermic and non-spontaneous reaction. A negative ΔS indicates the reactant in the transition state possesses a higher degree of ordered geometry than in its ground state. The immobilized catalysts provided great advantages towards product separation and efficient biodiesel production. Highlights: 1. Effective catalytic transesterification assisted by the ultrasonication method was used for bi-odiesel production. 2. Magnetite nanoparticles synthesized by the co-precipitation method were used as heteroge-neous catalysts. 3. An immobilized enzyme (Rhizopus-oryzae) was embedded in the heterogeneous catalyst, as it is reusable and cost-effective. 4. The maximum biodiesel yield obtained from Kapok oil was 93 ± 1.04% by catalytic trans-esterification reactions.

Mutants with Enhanced Cellobiose-Fermenting Ability from Thermotolerant Kluyveromyces marxianus DMKU 3-1042, Which Are Beneficial for Fermentation with Cellulosic Biomass

Abstract: Several cellulose-hydrolysis enzymes are required for eco-friendly utilization of cellulose as renewable biomass, and it would therefore be beneficial if fermenting microbes can provide such enzymes without genetic engineering. Thermotolerant and multisugar-fermenting Kluyveromyces marxianus is one of the promising yeasts for high-temperature fermentation and has genes for putative oligosaccharide-degradation enzymes. Mutants obtained after multiple mutagenesis showed significantly higher activity than that of the parental strain for cellobiose fermentation. The efficient strains were found to have amino acid substitutions and frame-shift mutations in 26-28 genes including 3 genes for glucose transporters. These strains grown in a cellobiose medium showed higher β-glucosidase than that of the parental strain and greatly reduced glucose utilization. The introduction of KTH2 for a glucose transporter into one of the efficient mutants reduced the cellobiose fermentation activity of the mutant. The results suggest that release from glucose repression significantly promotes the uptake of cellobiose. Co-culture of one efficient strain and the parental strain allowed good fermentation of both glucose and cellobiose, suggesting that the efficient strains are useful for conversion of cellulosic biomass to ethanol.

Investigation of the Performance and Emission Characteristics of Diesel Engine Fueled with Biogas-Diesel Dual Fuel

Abstract: Due to the popularity of diesel engines, utilization of fossil fuel has increased. However, fossil fuel resources are depleting and their prices are increasing day by day. Additionally, the emissions from the burning of petroleum-derived fuel is harming the global environment. This work covers the performance and emission parameters of a biogas-diesel dual-fuel mode diesel engine and compared them to baseline diesel. The experiment was conducted on a single-cylinder and four-stroke DI diesel engine with a maximum power output of 2.2 kW by varying engine load at a constant speed of 1500 RPM. The diesel was injected as factory setup, whereas biogas mixes with air and then delivered to the combustion chamber through intake manifold at various flow rates of 2, 4, and 6 L/min. At 2 L/min flow rate of biogas, the results were found to have better performance and lower emission, than that of the other flow; with an average reduction in BTE, HC, and NOx by 11.19, 0.52, and 19.91%, respectively, and an average increment in BSFC, CO, and CO2 by 11.81, 1.05, and 12.8%, respectively, as compared to diesel. The diesel replacement ratio was varied from 19.56 to 7.61% at zero engine load and 80% engine load with biogas energy share of 39.6 and 16.59%, respectively.

Natural Gas Conversion and Organic Waste Gasification by Detonation-Born Ultra-Superheated Steam: Effect of Reactor Volume

Abstract: The pulsed detonation (PD) gun technology was applied for the autothermal high-temperature conversion of natural gas and atmospheric-pressure oxygen-free allothermal gasification of liquid/solid organic wastes by detonation-born ultra-superheated steam (USS) using two flow reactors of essentially different volume: 100 and 40 dm3. Liquid and solid wastes were waste machine oil and wood sawdust, with moisture ranging from 10 to 30%wt. It was expected that decrease in the reactor volume from 100 to 40 dm3, other conditions being equal, on the one hand, should not affect natural gas conversion but, on the other hand, could lead to an increase in the gasification temperature in the flow reactor and, correspondingly, to an increase in the product syngas (H2 + CO) quality. The PD gun was fed by natural gas–oxygen mixture and operated at a frequency of 1 Hz. As was expected, complete conversion of natural gas to product syngas in the PD gun was obtained with H2/CO and CO2/CO ratios equal to 1.25 and 0.25, irrespective of the reactor volume. Liquid and solid wastes were gasified to H2, CO, and CH4 in the flow reactors. The steady-state H2/CO and CO2/CO ratios in the syngas produced from waste machine oil were 0.8 and 0.5 for the 100-dm3 reactor and 0.9 and 0.2 for the 40-dm3 reactor, respectively, thus indicating the expected improvement in syngas quality. Moreover, the maximum mass flow rate of feedstock in the 40-dm3 reactor was increased by a factor of over 4 as compared to the 100-dm3 reactor. The steady-state H2/CO and CO2/CO ratios in the syngas produced from the fixed weight (2 kg) batch of wood sawdust were 0.5 and 0.8 for both reactors, and the gasification time in both reactors was about 5–7 min. The measured H2 vs. CO2 and CO vs. CO2 dependences for the syngas produced by the autothermal high-temperature conversion of natural gas and atmospheric-pressure allothermal gasification of liquid/solid organic wastes by USS at f = 1 Hz were shown to be almost independent of the feedstock and reactor volume due to high values of local instantaneous gasification temperature.

Numerical Investigation of Dual Fuel Combustion on a Compression Ignition Engine Fueled with Hydrogen/Natural Gas Blends

Abstract: The present work aims to assess the influence of the composition of blends of hydrogen (H2) and Natural Gas (NG) on Dual Fuel (DF) combustion characteristics, including gaseous emissions. The 3D-CFD study is carried out by means of a customized version of the KIVA-3V code. An automotive 2.8 L, 4-cylinder turbocharged diesel engine was previously modified in order to operate in DF NG–diesel mode, and tested at the dynamometer bench. After validation against experimental results, the numerical model is applied to perform a set of combustion simulations at 3000 rpm–BMEP = 8 bar, in DF H2/NG-diesel mode. Different H2–NG blends are considered: as the H2 mole fraction varies from 0 vol% to 50 vol%, the fuel energy within the premixed charge is kept constant. The influence of the diesel Start Of Injection (SOI) is also investigated. Simulation results demonstrate that H2 enrichment accelerates the combustion process and promotes its completion, strongly decreasing UHC and CO emissions. Evidently, CO2 specific emissions are also reduced (up to about 20%, at 50 vol% of H2). The main drawbacks of the faster combustion include an increase of in-cylinder peak pressure and pressure rate rise, and of NOx emissions. However, the study demonstrates that the optimization of diesel SOI can eliminate all aforementioned shortcomings.

Assessing NO2-Hydrocarbon Interactions during Combustion of NO2/Alkane/Ar Mixtures in a Shock Tube Using CO Time Histories

Abstract: Modern gas turbines use combustion chemistry during the design phase to optimize their efficiency and reduce emissions of regulated pollutants such as NOx. The detailed understanding of the interactions during NOx and natural gas during combustion is therefore necessary for this optimization step. To better assess such interactions, NO2 was used as a sole oxidant during the oxidation of CH4 and C2H6 (the main components of natural gas) in a shock tube. The evolution of the CO mole fraction was followed by laser-absorption spectroscopy from dilute mixtures at around 1.2 atm. The experimental CO profiles were compared to several modern detailed kinetics mechanisms from the literature: models tuned to characterize NOx-hydrocarbons interactions, base-chemistry models (C0–C4) that contain a NOx sub-mechanism, and a nitromethane model. The comparison between the models and the experimental profiles showed that most modern NOx-hydrocarbon detailed kinetics mechanisms are not very accurate, while the base chemistry models were lacking accuracy overall as well. The nitromethane model and one hydrocarbon/NOx model were in relatively good agreement with the data over the entire range of conditions investigated, although there is still room for improvement. The numerical analysis of the results showed that while the models considered predict the same reaction pathways from the fuels to CO, they can be very inconsistent in the selection of the reaction rate coefficients. This variation is especially true for ethane, for which a larger disagreement with the data was generally observed.

The German Cement Industry as a CO2 Source for Other Industries

Abstract: Cement production is responsible for about eight percent of global CO2 emissions. A potential use for CO2 is the production of synthetic fuels through power-to-X (PtX) processes. For this purpose, a potential analysis is performed in which the possibilities for CO2 avoidance and CO2 capture and utilization (CCU) in the cement manufacturing process are evaluated. Based on the potential analysis, three scenarios for the development of the German cement industry until 2050 are developed and displayed in geo-referenced form, yielding potential locations for PtX plants. Results show that it is unlikely that cement can be fully replaced by alternative construction methods or new types of binders from today’s perspective. Measures to reduce CO2 emissions in cement production are limited, especially due to the restricted possibilities to replace limestone as feedstock. In an intermediate scenario, CO2 emissions in cement production decrease by 35% until 2050 compared to the average value from the 2014–2018 reference period. For CCU to be introduced at cement plants, the additional costs must be compensated, either through revenues from CO2 certificates or economic and regulatory incentives.

Co-Solvent Assisted Hydrothermal Liquefaction of Algal Biomass and Biocrude Upgrading

Abstract: This study reports the hydrothermal liquefaction (HTL) of microalgae Spirulina platenesis in the presence of alcohol or formic acid co-solvents. HTL runs are performed in a 1.8-L batch reactor at 300 °C using an alcohol (methanol and ethanol) or formic acid co-solvent. Consequently, hydrodeoxygenation (HDO) of resultant algal biocrude is performed at 350 °C for 2 h under high hydrogen pressure (~725 psi) using the Ru/C catalyst. The HTL results are compared with the control HTL run performed in water only. The results of the study show that the addition of co-solvents leads to a 30–63% increased biocrude yield over the control HTL run. Formic acid results in a 59.0% yield of biocrude, the highest amongst all co-solvents tested. Resultant biocrudes from formic acid-assisted and ethanol-assisted HTL runs have 21.6% and 3.8–11.0% higher energy content, respectively, than that of the control run. However, that of the methanol-assisted HTL results in biocrude with 4.2–9.0% lower energy density. Viscosity of biocrude from methanol- or ethanol-assisted HTL is higher than the control HTL but formic acid-assisted HTL results in a less viscous biocrude product. In addition, the HDO study leads to a 40.6% yield of upgraded oil, which is characterized by a higher net energy content and lower O/C and N/C ratios when compared to the initial HTL biocrude.

Optimization of Solid-State Fermentation of Switchgrass Using White-Rot Fungi for Biofuel Production

Abstract: Biological delignification using white-rot fungi is a possible approach in the pretreatment of lignocellulosic biomass. Despite the considerable promise of this low-input, environmentally-friendly pretreatment strategy, its large-scale application is still limited. Therefore, understanding the best combination of factors which affect biological pretreatment and its impact on enzymatic hydrolysis is essential for its commercialization. The present study was conducted to evaluate the impact of fungal pretreatment on the enzymatic digestibility of switchgrass under solid-state fermentation (SSF) using Phanerochaete chrysosporium (PC), Trametes versicolor 52J (Tv 52J), and a mutant strain of Trametes versicolor that is cellobiose dehydrogenase-deficient (Tv m4D). Response surface methodology and analysis of variance (ANOVA) were employed to ascertain the optimum pretreatment conditions and the effects of pretreatment factors on delignification, cellulose loss, and total available carbohydrate (TAC). Pretreatment with Tv m4D gave the highest TAC (73.4%), while the highest delignification (23.6%) was observed in the PC-treated sample. Fermentation temperature significantly affected the response variables for the wild-type fungal strains, while fermentation time was the main significant factor for Tv m4D. The result of enzymatic hydrolysis with fungus-treated switchgrass at optimum pretreatment conditions showed that pretreatment with the white-rot fungi enhanced enzymatic digestibility with wild-type T. versicolor (52J)-treated switchgrass, yielding approximately 64.9% and 74% more total reducing sugar before and after densification, respectively, than the untreated switchgrass sample. Pretreatment using PC and Tv 52J at low severity positively contributed to enzymatic digestibility but resulted in switchgrass pellets with low unit density and tensile strength compared to the pellets from the untreated switchgrass.

Performance of Citric Acid as a Catalyst and Support Catalyst When Synthesized with NaOH and CaO in Transesterification of Biodiesel from Black Soldier Fly Larvae Fed on Kitchen Waste

Abstract: Current research and development to lower the production cost of biodiesel by utilizing feedstock derived from waste motivates the quest for developing catalysts with high performance in transesterification. This study investigates the performance of citric acid as a catalyst and support catalyst in transesterification of oil from black soldier fly (Hermetia illucens) larvae fed on organic kitchen waste. Two catalysts were prepared by synthesizing citric acid with NaOH and CaO by a co-precipitation and an impregnation method, respectively. The design of the experiment adopted response surface methodology for the optimization of biodiesel productivity by varying: the percentage loading weight of citric acid, the impregnation temperature, the calcinating temperature and the calcinating time. The characteristic activity and reuse of the synthesized catalysts in transesterification reactions were investigated. The morphology, chemical composition and structure of the catalysts were characterized by scanning electron microscopy (SEM), Fourier transform infrared (FTIR) spectroscopy, X-ray fluorescence (XRF) and X-ray diffraction (XRD). High citric acid loading on NaOH and a small amount of citric acid on CaO resulted in improved dispersion and refinement of the particle sizes. Increasing citric acid loading on NaOH improved the CaO and SiO2 composition of the modified catalyst resulting in higher biodiesel yield compared to the modified CaO catalyst. A maximum biodiesel yield of 93.08%, ±1.31, was obtained when NaOH was synthesized with a 130% weight of citric acid at 80 °C and calcinated at 600 °C for 240 min. Comparatively, a maximum biodiesel yield of 90.35%, ±1.99, was obtained when CaO was synthesized with a 3% weight of citric acid, impregnated at 140 °C and calcinated at 900 °C for 240 min. The two modified catalysts could be recycled four times while maintaining a biodiesel yield of more than 70%.

CO Oxidation Capabilities of La- and Nd-Based Perovskites

Abstract: Catalytic tests to assess the performance of mixed perovskite-type oxides (La0.9Ca0.1FeO3-δ, La0.6Ca0.4FeO3-δ, Nd0.9Ca0.1FeO3-δ, Nd0.6Ca0.4FeO3-δ, Nd0.6Ca0.4Fe0.9Co0.1O3-δ, Nd0.6Ca0.4Fe0.97Ni0.03O3-δ, and LSF) with respect to CO oxidation are presented as well as characterization of the materials by XRD and SEM. Perovskites are a highly versatile class of materials due to their flexible composition and their ability to incorporate dopants easily. CO oxidation is a widely used “probe reaction” for heterogeneous catalysts. In this study, it is demonstrated how tuning the composition of the catalyst material (choice of A-site cation, A-site and B-site doping) greatly influences the activity. Changing the A-site cation to Nd3+ or increasing the concentration of Ca2+ as A-site dopant improves the performance of the catalyst. Additional B-site doping (e.g., Co) affects the performance as well—in the case of Co-doping by shifting ignition temperature to lower temperatures. Thus, perovskites offer an interesting approach to intelligent catalyst design and tuning the specific properties towards desired applications.

Effects of Injector Nozzle Number of Holes and Fuel Injection Pressures on the Diesel Engine Characteristics Operated with Waste Cooking Oil Biodiesel Blends

Abstract: This work covers the impact of varying injector nozzle hole numbers (INHNs) and fuel injection pressures (IPs) on fuel atomization, performance, and exhaust emission characteristics of a diesel engine. The primary goal of this research was to improve fuel characteristics. Increasing INHNs and fuel IPs have a substantial impact on the blended fuel viscosity and density, which leads to increased atomization and mixing rates, as well as combustion and engine efficiency. The fuel atomization was checked by varying the INHNs with an operating diesel fuel using the ANSYS Fluent spray simulation work. The experimental test was performed on the fuel blends of waste cooking oil (WCO)–diesel blends from 10 to 30% (with an increment of 10%) by evaluating the performance and emission parameters. The fuel IPs were altered on four, such as 190, 200 (default), 210, and 220 bar with a modification of INHN of 1 (default), 3, and 4), each 0.84, 0.33, and 0.25 mm in orifice size, respectively. The simulation result shows that the INHN-4 has better fuel atomization. Whereas the experimental test revealed that the increment in blending ratio of WCO was up to 30%, INHNs and fuel IPs enhanced the BSFC and BTE and reduced exhaust emissions. The results indicate that increasing the fuel IP up to 210 bar with a 4-hole INHN for B30 was the optimal combination for the overall enhancement of BSFC and BTE, as well as lower CO and HC emissions with a minor rise in NOx when compared to the baseline diesel.

Elemental Mapping and Characterization of Petroleum-Rich Rock Samples by Laser-Induced Breakdown Spectroscopy (LIBS)

Abstract: The application of Laser-Induced Breakdown Spectroscopy (LIBS) is presented for the direct elemental analysis of hydrocarbon-rich solids. In recent years, LIBS has become a powerful tool for obtaining elemental information and mapping analysis of different petroleum-rich samples with minimal to no sample preparation and without the need to separate the organic matter from the inorganic matter. By selecting the most intense and representative lines, the element distribution in a 2D map can be accessed in less than ten hours. For this reason, two types of hydrocarbon-rich solids were chosen for examination, i.e., core and shale. Nineteen elements were identified in the samples, and 2D mapping for Ca, Mg, Fe, Ti, Ni, C, H, K, O, and S is presented here. A detailed distribution of the elements, and the main components of the hydrocarbons present in these samples, were determined using LIBS. The H/C molar ratio was determined by building H and C calibration curves using data obtained from classical elemental analysis via combustion. These calibration curves contained a high degree of linearity (R2 > 0.98) with the limits of detection for C (193 nm), C (247 nm), and H (656 nm) of 848 mg kg−1, 353 mg kg−1, and 3.5 mg kg−1, respectively. By combining all of this information, LIBS allowed us to determine how these elements were spatially distributed, which elements were dominant in a given sample, and how much hydrocarbon was present, as well as providing a quantitative determination of the H/C molar ratio, and its correlation with the source of origin.

Process Simulation and Design Considerations for Biodiesel Production from Rubber Seed Oil

Abstract: Indonesia is one of the largest rubber producers worldwide. However, rubber seeds still garner less attention due to their low economic value. In fact, the rubber seeds contain 40–50% (w/w) of rubber seed oil (RSO), which is a potential candidate to be used as a feedstock in biodiesel production. In this regard, this study aims to model and simulate the production process of biodiesel from RSO via transesterification reaction, employing methanol and heterogeneous catalyst. The simulation was performed using ASPEN Hysys v11. Acid-based catalyzed esterification was implemented to eliminate soap formation, which may significantly lower biodiesel yield. The results showed that an RSO inlet rate of 1100 L/h with a methanol to oil molar ratio of 1:6 could generate around 1146 L/h biodiesel. Methanol recovery was conducted, an approximately 95% of excess methanol could be regenerated. Simulation results indicated that the properties of the biodiesel produced are compatible with modern diesel engines. Economic analysis also shows that this technology is promising, with excellent investment criteria.

Activation of CO2 on the Surfaces of Bare, Ti-Adsorbed and Ti-Doped C60

Abstract: There is a growing interest in finding a suitable catalyst for the adsorption and activation of CO2 molecules to minimize the effect of global warming. In this study, density functional theory-based simulations are employed to examine the adsorption and activation of a CO2 molecule on the pure, Ti-supported and Ti-doped surfaces of C60. The adsorption on the pure surface is very week. Adsorption becomes significant on the Ti-supported C60 surface together with significant activation. Such strong adsorption is evidenced by the significant charge transfer between Ti and C60. The Ti-doped C60 surface adsorbs weakly, but the activation is not significant.

Process Analysis and Design Considerations of a Low Carbon Methanol Synthesis Plant from Lignite/Waste Gasification

Abstract: This study presents design considerations and an evaluation of a full-scale process chain for methanol and advanced drop-in fuel production derived from lignite/solid recovered fuel (SRF) feedstock. The plant concept consists of a high-temperature Winkler (HTW) gasifier coupled with an air separation unit (ASU), which provides a high-purity (99.55%) gasification oxidant agent. The concept includes the commercially proven acid gas removal (AGR) system based on cold methanol (e.g., Rectisol® process) for the removal of BTX and naphthalene components. With the involvement of Rectisol®, an almost pure CO2 off-gas stream is generated that can be further stored or utilized (CCS/CCU), and a smaller CO2 stream containing H2S is recovered and subsequently driven to the sulfur recovery unit (e.g., Claus process). One of the potential uses of methanol is considered, and a methanol upgrading unit is implemented. The overall integrated process model was developed in the commercial software Aspen PlusTM. Simulations for different feedstock ratios were investigated, ensuring the concept’s adaptability in each case without major changes. A number of parametric studies were performed concerning (a) the oxygen purity and (b) the reformer type, and a comparison against alternative methanol production routes was conducted. Simulations show that the proposed system is able to retain the cold gas efficiency (CGE) in the range of 79–81.1% and the energetic fuel efficiency (EFE) at around 51%. An efficient conversion of approximately 99.5% of the carbon that enters the gasifiers is accomplished, with around 45% of carbon being captured in the form of pure CO2. Finally, the metrics of EFE and total C for the conversion of methanol to liquid fuels were 40.7% and 32%, respectively, revealing that the proposed pathway is an effective alternative for methanol valorization.

Modelling of an Anaerobic Digester: Identification of the Main Parameters Influencing the Production of Methane Using the Sobol Method

Abstract: Anaerobic digestion is a promising method of organic waste valorisation, particularly for fish farm waste, which has experienced a high growth rate in recent years. The literature contains predictive mathematical models that have been developed by various authors, allowing the prediction of the composition of bio-gas production from organic waste. In general, Monod’s kinetic expression is the basis for describing the enzymatic reaction rates for anaerobic digestion. In this work, several parameters are taken into account, such as temperature, cell growth inhibition, and other operating parameters, and systems of differential equations coupling the kinetics and stoichiometry for bio-reactions are applied to better describe the dynamics. Because of the high number of initial parameters that need to be defined for the anaerobic digester, the use of this model requires significant resources and a long calculation time. For this reason, a global sensitivity analysis (GSA) is applied to this predictive model based on the Sobol index method, in order to identify the most influential key parameters and the interactions between them. For the digestion of fish waste, it is observed that the key parameters influencing methane production are the lipid concentration of the waste, temperature, and hydraulic retention time (HRT).

A Ten-Year Study on Alkali Content of Coal Fly Ash

Abstract: After years of decline, coal consumption has risen significantly in the last year (2021), driven mainly by the ever-increasing demand in fast-growing Asian countries and fostered by rising gas prices in Europe and the United States. Coal is both the largest electricity production source and the largest source of carbon dioxide emission. Coal-fired plants produce electricity by generating steam by burning coal in a boiler, but also large amounts of coal fly ash. Coal fly ash contains essential constituents for cement production, such as Ca, Si, Al, and Fe. Application of coal-fired ash to produce clinker at high doses may reduce the limestone content in the raw mix. Furthermore, coal fly ash is one of the industrial source materials utilized in the development of low-carbon cements and concretes on account of its chemical characteristics. The monitoring methodology is based fundamentally on the analysis of a set of variables (Na2Oe, Na2O, K2O, free CaO, and reactive silica content and fineness) over time. Weak relations between Na2O and K2O, and Na2Oe, and reactive silica content were found. This applied research has been done to verify previously done research. The scope of this paper is to assess the alkaline content of coal fly ash over a period of 10 years. The Na2O-equivalent of coal fly ash ranged from 0.35% to 2.53%, with an average value of 0.79%. These values should be taken into account producing concretes made with potentially reactive aggregates in order to mitigate the alkali–silica reaction (ASR).

Characterization Techniques Coupled with Mathematical Tools for Deepening Asphaltene Structure

Abstract: Asphaltenes are the heavy fraction of fossil fuels, whose characterization remains a very difficult and challenging issue due to the still-persisting uncertainties about their structure and/or composition and molecular weight. Asphaltene components are highly condensed aromatic molecules having some heteroatoms and aliphatic functionalities. Their molecular weights distribution spans in a wide range, from hundreds to millions of mass units, depending on the diagnostic used, which is mainly due to the occurrence of self-aggregation. In the present work, mass spectrometry along with size exclusion chromatography and X-ray diffraction analysis have been applied to asphaltenes for giving some further insights into their molecular weight distribution and structural characteristics. Relatively small polycyclic aromatic hydrocarbons (PAHs) with a significant degree of aliphaticity were individuated by applying fast Fourier transform (FFT) and double bond equivalent (DBE) number analysis to the mass spectra. X-ray diffraction (XRD) confirmed some aliphaticity, showing peaks specific of aliphatic functionalities. Size exclusion chromatography indicated higher molecular weight, probably due to the aliphatic substituents. Mass spectrometry at high laser power enabled observing a downward shift of molecular masses corresponding to the loss of about 10 carbon atoms, suggesting the occurrence of aryl-linked core structures assumed to feature asphaltenes along with island and archipelago structures.

Influence of Transesterification Catalysts Synthesized with Citric Acid on the Quality and Oxidative Stability of Biodiesel from Black Soldier Fly Larvae

Abstract: In biodegradable waste management, use of Black Soldier Fly Larvae (BSFL) is a promising method for bioconversion of waste into crude insect fat as feedstock for biodiesel production. Biodiesel is a renewable alternative to fossil fuel, but it is more susceptible to oxidative degradation over long-term storage. This study investigates the effectiveness of NaOH and CaO catalysts synthesized with citric acid (CA) in improving the oxidative stability of biodiesel. The biodiesel and biodiesel/diesel blends derived from BSFL were stored at 63 °C for 8 days. The quality of biodiesel was determined by analysis of the physicochemical and fuel properties by: Fourier transform infrared (FTIR) spectroscopy, ultraviolet visible spectrophotometer (UV-Vis), gas chromatography-mass spectroscopy (GC-MS), bomb calorimeter and titration methods. Properties that were analyzed included: peroxide value, acid value, iodine value, refractive index, density, calorific value, total oxidation (TOTOX), anisidine value and fatty acid profile. The results showed that catalysts synthesized with CA retarded the decomposition of unsaturated fatty acids, resulting in a significant delay in the formation of hydroperoxides. Besides, 10-oxo-octadecanoic acid, an antioxidant, was present in biodiesel produced using catalysts synthesized with CA, hence enhancing the stability of biodiesel against oxidation. Catalysts synthesized with CA slowed the decomposition of monounsaturated fatty acids by 6.11–11.25%. Overall, biodiesel produced using catalysts synthesized with CA was observed to degrade at a slower rate than biodiesel produced using commercial calcium oxide. The reduced degradation rates demonstrate the effectiveness of the synthesized catalysts in enhancing the oxidation stability and consequently the fuel qualities of biodiesel from BSFL under accelerated storage.

Nuclear Magnetic Resonance (NMR) Outputs Generation for Clastic Rocks Using Multi Regression Analysis, Examples from Offshore Western Australia

Abstract: A large database of nuclear magnetic resonance (NMR) logging data from clastic rocks of offshore oil and gas fields of Western Australia was used to assess the performance of multi regression analysis (MRA) to calculate NMR log outputs from conventional well logs. This short paper introduces a set of MRA equations for the calculation of the NMR log outputs using conventional well logs as inputs. This study shows that unlike machine learning methods the MRA approach fails to predict most of the NMR log outputs with acceptable accuracy but can provide Coates and SDR permeabilities with R2 of more than 0.75.

Investigating the Effect of Volatiles on Sub-23 nm Particle Number Measurements for a Downsized GDI Engine with a Catalytic Stripper and Digital Filtering

Abstract: Recent efforts of both researchers and regulators regarding particulate emissions have focused on the contribution and presence of sub-23 nm particulates. Despite being previously excluded from emissions legislation with the particle measurement programme (PMP), the latest regulatory proposals suggest lowering the cut-off sizes for counting efficiencies and the use of catalytic strippers to include solid particles in this size range. This work investigated particulate emissions of a 1.0 L gasoline direct injection (GDI) engine using a differential mobility spectrometer (DMS) in combination with a catalytic stripper. Direct comparison of measurements taken with and without the catalytic stripper reveals that the catalytic stripper noticeably reduced variability in sub-23 nm particle concentration measurements. A significant portion of particles in this size regime remained (58–92%), suggesting a non-volatile nature for these particles. Digital filtering functions for imposing defined counting efficiencies were assessed with datasets acquired with the catalytic stripper; i.e., particle size distributions (PSDs) with removed volatiles. An updated filtering function for counting efficiency thresholds of d65 = 10 nm and d90 = 15 nm showed an increase in particulate numbers between 1.5% and up to 11.2%, compared to the closest previous digital filtering function. However, this increase is highly dependent on the underlying PSD. For a matrix of operating conditions (1250 to 2250 rpm and fast-idle to 40 Nm brake torque), the highest emissions occurred at fast-idle 1250 rpm with 1.93 × 108 #/cm3 using the updated filtering function and catalytic stripper. This setup showed an increase in particulate number of +27% to +390% over the test matrix when compared to DMS measurements without the catalytic stripper and applied counting efficiency thresholds of d50 = 23 nm and d90 = 41.